CN104956508B - Solution process organic semiconducting materials and organic semiconductor equipment - Google Patents

Solution process organic semiconducting materials and organic semiconductor equipment Download PDF

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CN104956508B
CN104956508B CN201480005535.6A CN201480005535A CN104956508B CN 104956508 B CN104956508 B CN 104956508B CN 201480005535 A CN201480005535 A CN 201480005535A CN 104956508 B CN104956508 B CN 104956508B
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dntt
compound
solution process
semiconducting materials
branched alkyl
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CN104956508A (en
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泷宫和男
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/484—Insulated gate field-effect transistors [IGFETs] characterised by the channel regions

Abstract

Solution process organic semiconducting materials are represented with formula 1.In formula 1, Y1And Y2It is separately chalcogen, R1And R2One be branched alkyl, another be hydrogen.

Description

Solution process organic semiconducting materials and organic semiconductor equipment
Technical field
The present invention relates to solution process organic semiconducting materials and organic semiconductor equipment.
Background technology
Make use of the organic semi-conductor membrane equipment such as organic FET equipment, organic el device to attract attention in recent years and by It is practical.As organic semiconducting materials, study, develop various compounds, such as dinaphtho thienothiophene (is below DNTT excellent charge mobility) is presented and (patent text is attracted attention as the material for showing organic semiconducting materials characteristic Offer 1,2).
Prior art literature
Technical literature
Patent document 1：International Publication No. 2008/050726
Patent document 2：International Publication No. 2010/098372
The content of the invention
Invent problem to be solved
DNTT derivatives disclosed in patent document 1 and 2 lack dissolubility in organic solvent.Accordingly, there exist can not The problem of organic semiconductor layer is manufactured based on solution process such as rubbing methods.
The present invention be in view of above-mentioned item and complete, it is therefore intended that there is provided in organic solvent it is soluble it is excellent, can With based on solution process such as rubbing methods come manufacture the solution process organic semiconducting materials utilized in organic semiconductor layer and Organic semiconductor equipment.
Solve the means of technical problem
Solution process organic semiconducting materials involved by the first viewpoint of the present invention are characterised by, include the table of formula 1 The compound shown.
[chemical formula 1]
(in formula 1, Y1And Y2It is separately chalcogen, R1And R2One be branched alkyl, another be hydrogen.)
Additionally, it is preferred that the main chain of the branched alkyl is more than C3.
Additionally, it is preferred that the main chain of the branched alkyl is more than C6.
Additionally, it is preferred that the side chain of the branched alkyl is more than C2.
Additionally, it is preferred that the side chain of the branched alkyl is bonded to the carbon of main chain more than 2.
Additionally, it is preferred that the side chain of the branched alkyl is bonded to the carbon of main chain more than 3.
Additionally, it is preferred that the Y1And Y2For sulphur atom or selenium atom.
Organic semiconductor equipment involved by the second viewpoint of the present invention is characterised by, includes the first viewpoint of the present invention Involved solution process organic semiconducting materials.
Invention effect
Solution process involved in the present invention organic semiconducting materials in organic solvent soluble excellent.Therefore, Organic semiconductor layer can be manufactured based on solution process such as rubbing methods.
Brief description of the drawings
[Fig. 1] is outside the absorption spectrum (Fig. 1 (A)), photoelectron spectroscopy (Fig. 1 (B)), face for represent 2,9-EH-DNTT films XRD (Fig. 1 (C)) chart.
[Fig. 2] is outside the absorption spectrum (Fig. 2 (A)), photoelectron spectroscopy (Fig. 2 (B)), face for represent 2-2-EH-DNTT films XRD (Fig. 2 (C)) chart.
[Fig. 3] is transmission characteristic (Fig. 3 (A)), the output characteristics (Fig. 3 (B)) for representing 2-2-EH-DNTT transistor units Chart.
[Fig. 4] is transmission characteristic (Fig. 4 (A)), the chart of output characteristics (Fig. 4 (B)) for representing ODTS treatment elements.
Embodiment
(solution process organic semiconducting materials)
Solution process organic semiconducting materials involved by present embodiment include the compound that formula 1 is represented.
[chemical formula 2]
In formula 1, Y1And Y2It is separately chalcogen (oxygen, sulphur, selenium, tellurium).Y1And Y2Preferably sulphur atom, selenium are former Son.In addition, Y1And Y2Preferably identical.
In addition, in formula 1, R1And R2One be branched alkyl, another is hydrogen.The main chain of branched alkyl be preferably C3 with On, more preferably more than C6.In addition, the side chain of branched alkyl is more than C1, more preferably more than C2.In addition, the preferred key of side chain Together in the main chain carbon of more than 2, the carbon of main chain more than 3 is more preferably bonded to.Side chain is thus intermolecular mutual away from condensed ring Effect is increased, and carrier mobility is improved.In addition, branched alkyl is preferably saturation branched alkyl.
Although it is believed that the carbon number of branched alkyl is more, dissolubility in organic solvent more increases, but implements described later In example, the carbon number of main chain shows very good dissolubility for C6, in addition, if branched alkyl is long, it is likely that manufacture has Piling up property during machine semiconductor layer is deteriorated, so as to cause characteristic of semiconductor to reduce, it is thus regarded that the carbon number of main chain be preferably C10 with Under.
It should illustrate, in formula 1, R1And R2Any of be straight chained alkyl, another for hydrogen compound in the case of, should Compound lacks dissolubility in organic solvent.Therefore, it is unsuitable for utilizing the solution process such as rubbing method manufacture organic semiconductor Layer.
In addition, in formula 1, R1And R2In the case that the two is the compound of branched alkyl, dissolubility in organic solvent is good It is good, on the other hand, transistor characteristic is not shown by the organic semiconductor layer of the manufactures such as rubbing method using the compound, so that can not Organic semiconducting materials as solution process.
The compound that above-mentioned formula 1 is represented is referred to patent document 1, known method disclosed in patent document 2 etc. and come Synthesis.It for example can in the following manner synthesize, but be not limited to this.
As represented by following reaction schemes 1, first, by 6- halo -2- methoxynaphthalenes or 7- halo -2- methoxynaphthalenes (compound (A)) synthesizes 6- alkyl -2- methoxynaphthalenes or 7- alkyl -2- methoxynaphthalenes (compound (B)).Can be by making chemical combination The Grignard reagent of thing (A) and the alkyl bromination magnesium with branched alkyl etc. is reacted to synthesize.
Then, synthesis compound (C).The synthesis of compound (C) can be by carrying out compound (B) and dimethyl sulphide etc. React to synthesize.
Then, synthesis compound (D).It can be synthesized by being reacted compound (C) and Boron tribromide etc..
Then, synthesis compound (E).It can be synthesized by making compound (D) be reacted with trifluoromethanesulfonic acid.
It should illustrate to illustrate, in compound (A), one of X1 and X2 is halogen atom, and another is hydrogen.In addition, In compound (B)~(E), R1And R2One be branched alkyl, another is hydrogen.
[chemical formula 3]
Reaction scheme 1
In addition, as represented by following reaction schemes 2, by 2- methoxynaphthalenes (compound (F)), via compound (G), changing Compound (H) synthesis compound (I).The synthesis of compound (G), compound (H) and compound (I) can respectively with above-claimed cpd (C), compound (D), the synthesis of compound (E) are similarly synthesized.
[chemical formula 4]
Reaction scheme 2
Then, as represented by following reaction schemes 3, by the way that above-mentioned two compound (compound (E), (I)) is condensed To synthesize compound (J).Further by the way that compound (J) closed loop to be synthesized to the compound (K) as target compound.Can be with Synthesized by carrying out ring-closure reaction with iodine in chloroform.It should illustrate to illustrate, in compound (E), (J), (K), R1 And R2One be branched alkyl, another is hydrogen.
[chemical formula 5]
Reaction scheme 3
In above-mentioned synthetic method, as one, to Y in formula 11And Y2Synthesis example for the compound of sulphur atom is said It is bright, instead of above-mentioned dimethyl sulphide it can carry out Y in synthesis type 1 by using dimethyl selenide, dimethyl ether1And Y2It is former for selenium atom, oxygen The compound of son.
Solution process organic semiconducting materials include the compound that formula 1 is represented, the compound that formula 1 is represented is in organic solvent In dissolubility it is high.Thus it is possible to using the solution process organic semiconducting materials of the compound represented comprising formula 1, utilize The solution process such as the rubbing methods such as spin-coating method, ink-jet method, screen painting method, lithography, micro-contact-printing are organic to manufacture Semiconductor layer.In solution process, vacuum, the condition of high temperature can need not be formed as vapour deposition method, to be realized with a low cost big face Long-pending organic semiconductor layer.
As the solution process solvable organic solvent of organic semiconducting materials, for example, it can enumerate chloroform, dichloro The alcohol series solvents such as the halo such as methane, dichloroethanes hydrocarbon system solvent, methanol, ethanol, propyl alcohol, butanol, octafluoropentanol, five fluorine propyl alcohol etc. The ester series solvents such as fluoro alcohol series solvent, ethyl acetate, butyl acetate, ethyl benzoate, diethyl carbonate, toluene, hexyl benzene, two The aromatic hydrocarbon series solvents such as toluene, mesitylene, chlorobenzene, dichloro-benzenes, methoxybenzene, chloronaphthalene, methyl naphthalene, naphthane, acetone, first The ketone series solvents such as base ethyl ketone, methyl iso-butyl ketone (MIBK), cyclopentanone, hexamethylene, dimethylformamide, dimethyl acetamide, N- first Ether series solvent, octane, decane, the hexamethylenes such as the acid amides series solvents such as base pyrrolidones, tetrahydrofuran, diisobutyl ether, diphenyl ether Hydrocarbon system solvents such as alkane etc..
In addition, for solution process organic semiconducting materials, it is organic in order to improve in addition to the compound that formula 1 is represented Film making properties, doping of semiconductor layer etc., can be with additive package, other semi-conducting materials.
(organic semiconductor equipment)
Organic semiconductor equipment involved by present embodiment is using above-mentioned solution process organic semiconducting materials Equipment.As organic semiconductor equipment, for example, it can enumerate the field-effect transistor with organic semiconductor layer, airborne with having Flow luminaire of sub- transport layer and/or luminescent layer etc..Organic semiconductor equipment can utilize known various manufacturers Method is manufactured, and is not particularly limited.
Embodiment
As described in following, 2- (2- ethylhexyls) dinaphtho [2,3-b is periodically synthesized：2 ', 3 '-f] thieno [2,3-b] thiophene (being below 2-2-EH-DNTT).
(synthesis of 6- (2- ethylhexyls) -2- methoxynaphthalenes (following is compound 1))
[chemical formula 6]
Being added in tetrahydrofuran (being below THF) (30mL) has the bromo- 2- methoxynaphthalenes (7.14g, 30mmol) of 6- and Ni (dppp)Cl2In the solution of (813mg, 1.5mmol), the THF solution of 2- ethylhexyl magnesium bromides, backflow 24 are added at room temperature Hour.It should illustrate, for the THF solution of 2- ethylhexyl magnesium bromides, by the bromo- 2- ethyl hexyls bromides (9.0mL, 45mmol) of 1- It is added in THF (7.5mL) to prepare with magnesium (1.17g, 48mmol).
After cooling, with water (30mL) diluted mixture, the solid of unreacted magnesium and generation is filtered to remove.
Filtered fluid is extracted with ether (15mL × 3).Compound obtained by extracting is washed with salt solution (30mL × 3), magnesium sulfate is used Dry.It is dried under reduced pressure, obtains flaxen oily compound 1 (5.4g, yield 50%).
The determination data of obtained compound 1 is shown in following.
1H NMR(500MHz,CDCl3) δ 0.87 (t, J=7.1Hz, 3H), 0.92 (t, J=7.5Hz, 3H) 1.221.37 (m, 8H), 1.67 (sept, J=6.2Hz, 2H), 2.68 (t, J=6.6Hz, 2H), 3.93 (s, 3H), 7.13 (s, 1H), 7.16 (dd, J=8.8,2.6Hz, 1H), 7.31 (dd, J=8.6,1.3Hz, 1H), 7.53 (s, 1H), 7.67 (d, J=8.6Hz, 1H), 7.69 (d, J=8.6Hz, 1H),
13C NMR(126MHz,CDCl3)；δ11.2,14.5,23.4,23.6,25.8,29.2,32.7,40.5,41.4, 55.6,106.0,118.9,126.8,127.5,128.9,129.3,129.4,133.2,137.5,157.4；
EIMS (70eV) m/z=270 (M+).HRMS(APCI)Calcd for C19H26O:270.19782；Found: 270.19791.
(synthesis of 6- (2- ethylhexyls) -3- methylsulfany -2- methoxynaphthalenes (following is compound 2))
[chemical formula 7]
Being added in THF (2.7mL) has in compound 1 (730mg, 2.7mmol) solution, and positive fourth is added at -78 DEG C The 1.59M hexane solutions of base lithium (2.0mL, 3.2mmol).
The mixture was stirred at room temperature after 1 hour, at -78 DEG C add dimethyl disulfide (0.36mL, 4.1mmol).Then, the mixture of generation is stirred at room temperature 18 hours.
Saturated aqueous ammonium chloride (5mL) is injected the mixture into, is extracted with ether (5mL × 3).
Compound obtained by extraction is washed with salt solution (5mL × 3), dried with magnesium sulfate.It is concentrated under reduced pressure, obtained To the oily compound 2 (853mg, quant.) of almost gilvous.
It should illustrate, sample for analysis is by silica gel column chromatography (developing solvent：Dichloromethane/hexane (v/v=1：1, Rf =0.35)) isolate and purify to use.
The determination data of obtained compound 2 is shown in following.
1H NMR(500MHz,CDCl3) δ 0.87 (t, J=7.0Hz, 3H), 0.89 (t, J=7.2Hz, 3H) 1.25-1.36 (m, 8H), 1.64 (sept, J=6.6Hz, 2H), 2.55 (s, 1H), 2.66 (t, J=6.5Hz, 2H), 3.99 (s, 3H), 7.07 (s, 1H), 7.22 (d, J=8.3Hz, 1H), 7.42 (s, 1H) 7.47 (s, 1H), 7.62 (d, J=8.3Hz, 1H),
13C NMR(126MHz,CDCl3)；δ11.2,14.5,14.9,23.4,25.8,29.3,32.8,40.5,41.5, 56.2,105.0,123.2,126.3,126.5,127.9,129.6,129.7,130.7,128.0,154.3；
EIMS (70eV) m/z=316 (M+).HRMS(APCI)Calcd for C20H28OS:316.18554；Found: 316.18576.
(synthesis of 6- (2- ethylhexyls) -3- methylsulfanies -2 hydroxy naphthalene (following is compound 3))
[chemical formula 8]
Being added in dichloromethane (5mL) has in compound 2 (681mg, 2.2mmol) solution, and three are added dropwise at -78 DEG C The dichloromethane solution (about 2M, 1.1mL, 4.3mmol) of boron bromide.
Mixture was stirred at room temperature after 5 hours, is added in ice (about 2g).
Mixture it will be extracted obtained by purifying with dichloromethane (5mL × 3).
Organic phase is washed with salt solution (5mL × 3), is dried, concentrated under reduced pressure with magnesium sulfate.
By residue silica gel column chromatography (developing solvent：Dichloromethane/hexane (v/v=1/1, Rf=0.28)) carry out Isolate and purify, obtain the oily compound 3 (650mg, quant.) of yellow.
The determination data of obtained compound 3 is shown in following.
1H NMR(500MHz,CDCl3) δ 0.88 (t, J=6.9Hz, 3H), 0.91 (t, J=7.3Hz, 3H) 1.25-1.36 (m, 8H), 1.66 (sept, J=6.0Hz, 2H), 2.43 (s, 1H), 2.65 (t, J=6.4Hz, 2H), 6.60 (s, 1H), 7.26 (d, J=8.4Hz, 1H), 7.47 (s, 1H) 7.60 (d, J=8.4Hz, 1H), 7.95 (s, 1H),
13C NMR(126MHz,CDCl3)；δ11.2,14.5,20.2,23.4,02325.8,29.2,32.7,40.5, 41.3,109.4,124.4,126.5,127.0,129.4129.6,133.8(×2),137.8,152.4；IR(KBr)ν 3411cm-1(OH)；
EIMS (70eV) m/z=302 (M+).HRMS(APCI)Calcd for C19H26O:302.16989；Found: 302.17023.
(the conjunction of 6- (2- ethylhexyls) -3- methylsulfanies -2- (trifyl epoxide) naphthalene (following is compound 4) Into)
[chemical formula 9]
Being added in dichloromethane (7mL) has compound 3 (640mg, 2.1mmol) and pyridine (0.89mL, 6.4mmol) simultaneously In the solution deaerated, trifluoromethanesulfanhydride anhydride (0.7mL, 4.2mmol) is added at 0 DEG C.
It is stirred at room temperature after 25 minutes, after water (5mL) and hydrochloric acid (4M, 2mL) diluted mixture, uses dichloromethane (5mL × 3) are extracted.
Organic phase is washed with salt solution (5mL × 3), is dried, concentrated under reduced pressure with magnesium sulfate, obtain yellow oily almost pure Compound 4 (800mg, 87%).
The determination data of obtained compound 4 is shown in following.
1H NMR(500MHz,CDCl3) δ 0.87 (t, J=7.2Hz, 3H), 0.89 (t, J=7.5Hz, 3H) 1.24-1.36 (m, 8H), 1.67 (sept, J=6.4Hz, 2H), 2.59 (s, 3H), 2.67 (d, J=7.0Hz, 1H), 2.69 (d, d, J= 7.2Hz, 1H), 7.32 (dd, J=1.5,8.4Hz, 1H), 7.54 (s, 1H), 7.63 (s, 1H) 7.68 (s, 1H), 7.71 (d, J= 8.4Hz,1H),
13C NMR(126MHz,CDCl3)；δ11.1,14.5,16.2,23.4,25.8,29.2,32.7,40.7,41.4, (120.0,120.3 q, J=315Hz) 126.5,126.7,127.8,129.2,129.8,130.0,131.0,133.2,142.1, 145.2；
IR(KBr)ν1425,1210cm-1(-O-SO2-)；
EIMS(70eV),HRMS(APCI)Calcd for C20H25F3O3S2:434.11917；Found:434.11905.
(anti-form-1-(3- methylsulfany naphthalene-2- bases)-2- (6- (2- ethylhexyls)-3- methylsulfany naphthalene-2- bases) ethene The synthesis of (following is compound 5))
[chemical formula 10]
Being added in DMF (N,N-dimethylformamide) (48mL) has compound 4 (2.58g, 5.94mmol), 3- methyl sulphur Base -2- (trifyl epoxide) naphthalene (1.91g, 5.94mmol) and anti-form-1, double (tributylstamlyl) ethene of 2- In (3.6g, 5.94mmol) and the solution deaerated, Pd (PPh are added3)4(343mg, 0.3mmol, 5mol%).
The mixture is heated 24 hours in darkroom with 90 DEG C.Thereafter, it is diluted with water, uses chloroform extraction.
With salt water washing extract, dried, concentrated under reduced pressure with magnesium sulfate.
Residue is passed through into silicagel pad (developing solvent：Dichloromethane), obtain yellow solid compound 5 (910mg, 32%).
The determination data of obtained compound 5 is shown in following.
Mp 78-79℃；
1H NMR(500MHz,CDCl3) δ 0.88 (t, J=7.1Hz, 3H), 0.92 (t, J=8.6Hz, 3H), 1.24-1.38 (m, 8H), 1.67 (sept, J=7.4Hz, 1H), 2.60 (s, 1H), 2.69 (d, d, J=6.7,6.8Hz, 2H), 7.27 (s, 1H), 7.44 (tt, J=1.1,7.5Hz, 2H), 7.50 (s, 1H), 7.60 (s, 1H), 7.64 (s, 1H), 7.65 (s, 1H), 7.66 (d, J=7.5Hz, 1H), 7.74 (d, J=8.3Hz, 1H), 7.77 (d, J=8.3Hz, 1H), 7.85 (d, J=7.5Hz, 1H), 8.06(s,1H),8.09(s,1H)；
13C NMR(126MHz,CDCl3)；δ11.2,14.5,16.7,16.8,23.4,25.8,29.3,32.8,40.8, 41.4,124.3,124.5,125.3,125.4,126.0,126.4,126.8,126.9,128.0,128.2,128.3,128.4, 129.1,130.3,131.9,133.7,133.8,134.5,135.4,136.0,136.2,140.7；
EIMS (70eV) m/z=484 (M+).HRMS(APCI)Calcd for C32H36S2:484.22529；Found: 484.22568.
(2-2-EH-DNTT synthesis)
[chemical formula 11]
Compound 5 (720mg, 1.5mmol) and iodine (11g, 45mmol) are added in chloroform (15mL), at 80 DEG C Stirring 20 hours.
Add this mixture in aqueous solution of sodium bisulfite (20mL).
Thereafter, with chloroform extraction, with salt water washing extract, dried, concentrated under reduced pressure with magnesium sulfate.
With hexane wash residual thing, faint yellow solid 2-2-EH-DNTT (186mg, 28%) is obtained.
Obtained 2-2-EH-DNTT determination data is shown in following.
Mp>300℃；
1H NMR(500MHz,CDCl3) δ 0.88 (t, J=7.0Hz, 3H), 0.92 (t, J=7.4Hz, 3H), 1.26-1.38 (m, 8H), 1.72 (sept, J=6.4Hz, 1H), 2.74 (d, d, J=7.2,7.1Hz, 2H), 7.36 (d, J=8.4Hz, 1H) 7.52-7.54 (m, 2H), 7.67 (s, 1H), 7.94 (d, J=8.4Hz, 1H), 7.94-7.96 (m, 1H), 8.03-8.05 (m, 1H),8.33(s,1H),8.34(s,1H),8.36(s,1H),8.42(s,1H)；
13C NMR(126MHz,CDCl3)；δ11.2,14.5,23.3,25.9,29.2,32.8,40.8,41.2,120.2, 120.3,122.1,122.7,126.0,126.2,126.8,127.7,128.3,128.4,128.6,130.2,130.7, 131.6,131.7,132.0(×2),132.8,133.6,134.2,140.1,141.1；
EIMS (70eV) m/z=452 (M+).HRMS(APCI)Calcd for C30H28S2:452.16269；Found: 452.16248.
In addition, as comparative example, as described in following, periodically synthesize 2,9- bis- (2- ethylhexyls) dinaphtho [2, 3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (being below 2,9-EH-DNTT).
(anti-form-1, the conjunction of double (6- (2- ethylhexyls) -3- methylsulfany naphthalene -2- bases) ethene of 2- (following is compound 6) Into)
[chemical formula 12]
Being added in DMF (27mL) has compound 4 (1.48g, 3.4mmol) and anti-form-1, the double (tributylstannyls of 2- Base) Pd (PPh are added in ethene and the solution that is deaerated3)4(158mg, 0.13mmol, 4mol%).
The mixture is heated 24 hours in darkroom with 90 DEG C.Thereafter, it is diluted with water, uses chloroform extraction.
With salt water washing extract, dried, concentrated under reduced pressure with magnesium sulfate.
Residue is passed through into silicagel pad (developing solvent：Dichloromethane), obtain yellow solid compound 11 (880mg, 87%).
The determination data of obtained compound 6 is shown in following.
Mp 64-65℃；
1H NMR(500MHz,CDCl3) δ 0.87 (t, J=7.2Hz, 6H), 0.90 (t, J=7.4Hz, 6H) 1.25-1.37 (m, 16H), 1.69 (sept, J=6.1Hz, 4H), 2.59 (s, 2H), 2.67 (d, J=6.9Hz, 4H), 2.69 (d, J= 7.1Hz, 2H), 7.25 (d, J=8.4Hz, 2H), 7.49 (s, 2H), 7.59 (s, 2H), 7.64 (s, 2H) 7.75 (d, J= 8.4Hz,2H),8.01(s,2H),
13C NMR(126MHz,CDCl3)；δ11.2,14.5,17.8,23.4,25.8,29.3,32.8,40.8,41.4, 124.3,125.2,126.4,127.9,128.2,128.6,130.4,133.8,134.6,136.0,140.6；
EIMS (70eV) m/z=596 (M+).HRMS(APCI)Calcd for C40H52S2:596.35049；Found: 596.35077.
(2,9-EH-DNTT synthesis)
[chemical formula 13]
Compound 6 (2.2g, 3.7mmol) and iodine (28g, 111mmol) are added in chloroform (37mL), at 80 DEG C Stirring 20 hours.
Add this mixture in aqueous solution of sodium bisulfite (20mL).
Thereafter, with chloroform extraction, with salt water washing extract, dried, concentrated under reduced pressure with magnesium sulfate.
With hexane wash residual thing, faint yellow solid 2,9-EH-DNTT (966mg, 46%) are obtained.
Obtained 2,9-EH-DNTT determination data is shown in following.
Mp 218-219℃；
1H NMR(500MHz,CDCl3) δ 0.87 (t, J=7.1Hz, 6H), 0.92 (t, J=7.5Hz, 6H) 1.25-1.37 (m, 16H), 1.72 (sept, J=6.0Hz, 4H), 2.73 (d, J=6.7Hz, 2H), 2.74 (d, J=7.1Hz, 2H) 7.34 (d, J=8.5Hz, 2H), 7.65 (s, 2H), 7.92 (d, J=8.5Hz, 2H), 8.29 (s, 2H), 8.32 (s, 2H)；
13C NMR(126MHz,CDCl3)；δ11.2,14.5,23.4,25.9,29.2,32.8,40.8,41.3,120.1, 122.1,126.8,128.3(×2),130.2,132.1,133.7,140.0,141.1；
EIMS (70eV) m/z=564 (M+).HRMS(APCI)Calcd for C38H44S2:594.28789；Found: 594.28815.
In addition, as comparative example, 2- ethylhexyl magnesium bromides are replaced with into decyl magnesium bromide, in addition, with above-mentioned 2- 2-EH-DNTT synthesis is similarly carried out, synthesis 2- decyls-dinaphtho [2,3-b：2 ', 3 '-f] thieno [2,3-b] thiophene (being below 2-D-DNTT).
[chemical formula 14]
(2,9-D-DNTT synthesis)
In addition, as comparative example, 2- ethylhexyl magnesium bromides are replaced with into decyl magnesium bromide, in addition, and above-mentioned 2, 9-EH-DNTT synthesis is similarly carried out, synthesis 2,9- didecyls dinaphtho [2,3-b：2 ', 3 '-f] thieno [2,3-b] thiophene Fen (being below 2,9-D-DNTT).
[chemical formula 15]
(evaluation of solubility)
2-2-EH-DNTT, 2,9-EH-DNTT, 2-D-DNTT, 2,9-D-DNTT is set to be dissolved separately in the chloroform of room temperature In, determine solubility.It the results are shown in table 1.
[table 1]
Compound (2-2-EH-DNTT, 2,9-EH-DNTT) with branched alkyl shows good dissolubility.It is another Aspect, the compound (2-D-DNTT, 2,9-D-DNTT) with straight chained alkyl is not dissolved in a solvent, so as to understand cannot act as Coating organic semiconducting materials.
(evaluation of film physical property)
Film is made with the 2-2-EH-DNTT of favorable solubility in a solvent and 2,9-EH-DNTT, its physical property is evaluated.
(2-2-EH-DNTT films, the making of 2,9-EH-DNTT films, evaluation)
2-2-EH-DNTT is dissolved in the solution that 0.3g/L is prepared in chloroform, after being filtered through film filter, carried out The thick 2-2-EH-DNTT films of about 100nm are made by spin-coating method on the n-type silicon substrate of above-mentioned surface treatment.In addition, with 2, 9-EH-DNTT makes 2,9-EH-DNTT films as described above.
The absorption spectrum of 2,9-EH-DNTT films is shown in Fig. 1 (A).In the absorption spectrum of 2,9-EH-DNTT films, with Dinaphtho [2,3-b without substituent:2 ', 3 '-f] evaporation film of thieno [2,3-b] thiophene (being below DNTT) compares, Obvious shortwave long displacement can be observed.It can thus be appreciated that intermolecular interaction is weak under filminess.
In addition, the photoelectron spectroscopy of 2,9-EH-DNTT films is shown in into Fig. 1 (B).The 2,9- estimated according to photoelectron spectroscopy The ionization potential of EH-DNTT films is 5.7eV, then increases compared with unsubstituted DNTT 5.4eV.This can illustrate intermolecular phase Interaction weakens.
In addition, X-ray diffraction result outside the face of 2,9-EH-DNTT films is shown in into Fig. 1 (C).In Fig. 1 (C), although visible Crystal peak, but the interfloor distance of estimation is short for 16 angstroms, and molecular orientation can not say the form being desirable to.
Then, the absorption spectrum of 2-2-EH-DNTT films is shown in Fig. 2 (A).The absorption spectrum of 2-2-EH-DNTT films The absworption peak same with DNTT is shown, is compared with 2,9-EH-DNTT films, it is observed that clearly long wavelength shifted.This Show that the intermolecular interaction under filminess is being recovered compared with 2,9-EH-DNTT films.
In addition, the photoelectron spectroscopy of 2-2-EH-DNTT films is shown in into Fig. 2 (B).The film estimated according to photoelectron spectroscopy Ionization potential be 5.0eV, then the reduction with unsubstituted DNTT 5.4eV compared with, and is identical with asymmetric straight chained alkyl body , thus also imply that there is intermolecular interaction.
In addition, X-ray diffraction result outside the face of 2-2-EH-DNTT films is shown in into Fig. 2 (C).X-ray diffraction is seen outside face It is that molecular long axis is stood in the crystal structure oriented on real estate that the peak of survey, which implys that, and the interfloor distance of estimation is also 26 Angstrom, it is corresponding with the length also comprising the molecular long axis including alkyl.
(making, the evaluation of transistor unit)
Bottom filling transistor unit is made with the 2-2-EH-DNTT of above-mentioned favorable solubility and 2,9-EH-DNTT, and is evaluated Characteristic.
N-type silicon substrate as gate electrode, with silicon oxide layer thick 200nm, with high-concentration dopant is fully washed Afterwards, the silicon oxide layer surface of n-type silicon substrate is subjected to silane treatment with perfluoro decyl triethoxysilane (FDTS).
2-2-EH-DNTT is dissolved in the solution that 0.3g/L is prepared in chloroform, after being filtered through film filter, carried out The thick 2-2-EH-DNTT films of about 100nm are made by spin-coating method on the n-type silicon substrate of above-mentioned surface treatment.
The film is heated 30 minutes with 200 DEG C under nitrogen atmosphere.
The vacuum evaporation gold on 2-2-EH-DNTT films, forms source electrode and drain electrode.It is 50 to be so fabricated to flute length μm, groove width be 1.5mm bottom filling top contact transistor npn npn element.The transistor unit is remembered into transistor unit 2- below 2-EH-DNTT。
In addition, being carried out as described above with 2,9-EH-DNTT, bottom filling top contact transistor npn npn element is made.With Under, the transistor unit is remembered into transistor unit 2,9-EH-DNTT.
With 2-2-EH-DNTT, for the transistor unit 2-2-EH-DNTT being made, make gate voltage VgWith 20~- 60V, source and drain voltage across poles VdTransistor characteristic is determined with 0~-60V changes.Transmission characteristic is shown in Fig. 3 (A), output characteristics It is shown in Fig. 3 (B).Go out mobility by these property calculations for 0.3cm2/Vs。
On the other hand, for transistor unit 2,9-EH-DNTT, also attempt to carry out transistor characteristic as described above Determine, but for transistor unit 2,9-EH-DNTT, do not reply completely, it is known that worked not as transistor.By above-mentioned The physical property parsing of 2,9-EH-DNTT films, can obtain two ethylhexyl steric bulks greatly, therefore, hinder close molecule filling, Substantially reduce intermolecular interaction.Thus transistor unit 2 is also demonstrate that, 9-EH-DNTT is not replied, i.e. be injected into thin Carrier in film can not be migrated.
(2- (3- ethylheptyls) dinaphtho [2,3-b:2 ', 3 '-f] thieno [2,3-b] thiophene (is below 2-3-EH- DNTT synthesis))
2- ethylhexyl magnesium bromides are replaced with 3- ethylheptyl magnesium bromides, in addition, successively with the conjunction of above-claimed cpd 1 Into, the synthesis of compound 2, the synthesis of compound 3, the synthesis of compound 4, the synthesis of compound 5,2-2-EH-DNTT synthesis Similarly carry out, synthesize 2-3-EH-DNTT.
[chemical formula 16]
By obtain 2-3-EH-DNTT determination data be shown in it is following.
mp>300℃；
1H-NMR(500MHz,CDCl3) δ 0.90 (t, J=7.2Hz, 3H), 0.92 (t, J=6.6Hz, 3H), 1.25-1.43 (m, 9H), 1.67-1.73 (m, 2H), 2.80 (t, J=8.4Hz, 2H), 7.40 (dd, J=8.8and 1.5Hz, 1H), 7.52 (d, J=6.7Hz, 1H), 7.53 (d, J=6.4Hz, 1H), 7.71 (s, 1H), 7.94-7.97 (m, 1H), 7.96 (d, J= 8.8Hz,1H),8.03-8.05(m,1H),8.33(s,1H),8.35(s,1H),8.36(s,1H),8.43(s,1H)；
13C-NMR(126MHz,CDCl3)11.0,14.2,23.3,26.2,29.2,33.1,33.8,35.2,39.0, 120.1(x3),120.2,121.9,122.0,122.5,122.6,125.5,125.6,125.8(x2),126.0(x2), 127.5,127.7,127.8,128.4,128.5,130.2,131.6,131.7,132.0,132.1,132.7,133.5, 134.2,141.0,141.1,141.4(x2)；
EI-MS(70eV)m/z 466(M+)；HR-MS(APCI)m/z calcd for C31H31S2[M+H]+ 467.18617,found 467.18637；Anal.Calcd for C31H30S2C；79.78,H；6.48%.Found.C； 79.97,H；6.46%.
(evaluation of solubility)
2-3-EH-DNTT is dissolved in the chloroform of room temperature, determine solubility.2-3-EH-DNTT solubility is 0.67g/L is better than 2-2-EH-DNTT (0.43g/L).
(making, the evaluation of transistor unit)
Bottom filling top contact transistor npn npn element is made with 2-3-EH-DNTT, characteristic is evaluated.
N-type silicon substrate as gate electrode, with silicon oxide layer thick 200nm, with high-concentration dopant is fully washed Wash.
2-3-EH-DNTT is dissolved in the solution that 0.3g/L is prepared in chloroform, after being filtered through film filter, carried out The thick 2-3-EH-DNTT films of about 100nm are made by spin-coating method on the n-type silicon substrate of above-mentioned surface treatment.
The film is heated 30 minutes with 100 DEG C under nitrogen atmosphere.
The vacuum evaporation gold on 2-3-EH-DNTT films, forms source electrode and drain electrode.So make 40 μm of flute length, Groove width 3mm bottom filling top contact transistor npn npn element (Untreated elements).
In addition, after the washing of n-type silicon substrate, by 1,1,1,3,3,3- HMDS of silicon oxide layer surface (HMDS) silane treatment is carried out, bottom filling top contact transistor npn npn element (HMDS treatment elements) is made as described above.
In addition, after the washing of n-type silicon substrate, silicon oxide layer surface is carried out at silane with eight decyltrichlorosilanes (ODTS) Reason, makes bottom filling top contact transistor npn npn element (ODTS treatment elements) as described above.
In addition, silane treatment is carried out with octyltrichlorosilane (OTS) after the washing of n-type silicon substrate, by silicon oxide layer surface, Bottom filling top contact type body tube elements (OTS treatment elements) are made as described above.
For each transistor unit being fabricated to, make gate voltage VgWith 20~-60V, source and drain voltage across poles VdWith 0~- 60V changes determine transistor characteristic.By the carrier mobility (μ [cm of respective transistor unit2V-1s-1]), critical voltage (Vth[V]), on-off ratio (Ion/off) it is shown in table 2.In addition, substrate is carried out into the transistor member that silane treatment is made with ODTS The transmission characteristic of part is shown in Fig. 4 (A), output characteristics and is shown in Fig. 4 (B).Should illustrate, transistor unit make respectively 15 with On, the carrier mobility in table 2 represents its average value and peak (in parantheses).
[table 2]
In the transistor unit being fabricated to by 2-3-EH-DNTT, compared with transistor unit 2-2-EH-DNTT, carrier Mobility is improved.Especially for the ODTS elements being made to substrate progress ODTS processing, carrier mobility highest is 1.6cm2/ Vs is (average：1.02cm2/ Vs), show good transistor characteristic.It is thought that due to the side chain second of ethylheptyl Base is away from DNTT skeletons, so that bone lattice intermolecular interaction is improved.
Thought by result above, the molecule for importing branched alkyl only on a naphthalene as the compound that formula 1 is represented is set Meter is to meet both dissolubility and transistor in organic solvent characteristics and essential.
It should illustrate, the present invention carries out various embodiments and deformation with can not departing from the scope of the present invention. In addition, above-mentioned embodiment is used for, the present invention will be described, rather than limits the scope of the present invention.
The application is based in Japan's patent application filed in 22 days January in 2013 2013-9153, in August, 2013 Japan's patent application 2013-175678 filed in 27 days.By Japan's patent application 2013-9153, Japan's patent Specification, Patent right requirement, the accompanying drawing of application 2013-175678 are all quoted in this specification as reference.
Utilization in industry
As described above, the dissolubility of solution process involved in the present invention with organic semiconducting materials in a solvent is excellent, It therefore, it can, using the solution process such as rubbing method formation organic semiconductor layer, therefore, it can be used to manufacture field-effect transistor etc. Semiconductor device.

Claims (7)

1. a kind of solution process organic semiconducting materials, it is characterised in that the compound represented comprising formula 1,
In formula 1, Y1And Y2It is separately chalcogen, R1And R2One be branched alkyl, another be hydrogen,
The side chain of the branched alkyl is bonded to the carbon of main chain more than 2.
2. solution process organic semiconducting materials according to claim 1, wherein, the main chain of the branched alkyl is C3 More than.
3. solution process organic semiconducting materials according to claim 2, wherein, the main chain of the branched alkyl is C6 More than.
4. according to solution process organic semiconducting materials according to any one of claims 1 to 3, wherein, branched alkyl Side chain is more than C2.
5. solution process organic semiconducting materials according to claim 1, wherein, the side chain bonding of the branched alkyl In the main chain carbon of more than 3.
6. solution process organic semiconducting materials according to claim 1, wherein, the Y1And Y2For sulphur atom or selenium Atom.
7. a kind of organic semiconductor equipment, it is characterised in that used comprising solution process according to any one of claims 1 to 6 Organic semiconducting materials.
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